Fungi and bacteria resistant polyvinyl chloride compositions



Patented Sept. 11, 1951 FUNGI AND BACTERIA RESISTANT POLY- VVINYLCHLORIDE COMPOSITIONS Walter E. Field, St. Louis, Mo., asslgnor toMonsanto Chemical Company, St. Louis, Mo., a corporation of Delaware NoDrawing.

Claims. 1

This invention relates to improved resinous compositions containingpolymerized vinyl chloride. More particularly, this invention relates toplasticized resinous compositions having improved resistance todeterioration due to attack by such micro-organisms as fungi andbacteria, and con taining polymerized vinyl chloride, copolymerscontaining predominantly combined vinyl chloride, or combinationsthereof containing predominantly combinedvinyl chloride, collectivelyand broadly herein referred to as polyvinyl chloride compositions."

Polyvinyl chloride compositions have found many useful applicationsbecause of their wide range of elastomeric and mechanical propertiescoupled with their extreme resistance to oxidation, organic solvents,acids and alkalies. Typical of such applications are calender'ed filmsand sheeting for wearing apparel, shower curtains and seat and cushioncoverings. In such applications, polyvinyl chloride compositions havefound utility as a free or unsupported film but more frequentlypolyvinyl chloride compositions have been used to coat such textiles ascotton, wool, silk, rayon, and nylon thereby obtaining a composition orfabric for use in the above mentioned applications which combines thedesirable properties of the textile and the desirable properties of thepolyvinyl chloride composition. Such polyvinyl chloride compositionsfrequently contain plasticizers or stabilizers which have their originin animal or vegetable sources, or the base material of coatedcompositions frequently contains materials which have their origin inanimal or vegetable sources which thereby render the resultantcomposition quite susceptible to deteriorating attack by suchmicro-organisms as fungi and bacteria; Such deterioration of polyvinylchloride compositions or polyvinyl chloride coated compositions seriouslhinders full scale utility of the compositions particularly in thoseareas and those applications which are conducive to such an attack.

Copper B-quinolinolate is a well known fungicide and bactericide, andrepeated attempts have been made to incorporate this material intopolyvinyl chloride compositions in order to render suchcompositionsresistant to attacks by fungi and bacteria. It has beenfound, however, that copper a-quinolinolate is exceedingly incompatiblewith polyvinyl chloride compositions. According to the methods asheretofore practiced, if even minor amounts, of the order of 0.2% byweight of total composition, are incorporated into aplasticizedpolyvinyl chloride composition, within sev- ApplicationDecember 6, 1948, Serial No; 63,857

2 eral hours after preparation oi the composition the copper8-quinolinolate begins to crystallize or bloom on the surface of thecomposition indicating incompatibility and rendering the compositionunfit for use.

It is an object of this invention to provide polyvinyl chloridecompositions having improved resistance to deterioration due to attackby such micro-organismsas fungi and bacteria,

It is also an object of this invention to provide a plasticizedpolyvinyl chloride composition wherein there may be incorporated asuflicient quantity of copper 8-quinolinolate to render the compositionresistant to attack by fungi and bacteria, and in which composition thecopper il-quinolinolate is fully compatible evidencing no tendency tobloom or crystallize in the composition.

It is a. further object of this invention to provide a textile coatedwith a plasticized polyvinyl chloride composition which is resistant todeterioration due to attack by fungi and bacteria.

Further objects will become apparent from the description of the novelcompositions of this invention and the claims.

In order to obtain fungi or bacteria resistant polyvinyl chloridecompositions, it is desired that such compositions contain from 0.1 to2.5 parts by weight of copper B-quinolinolate per hundred parts ofpolymerized vinyl chloride resin. It has now been found that suchquantities of copper 8-quinolinolate may be incorporated into apolyvinyl chloride composition without blooming or crystallizationresulting if there is also incorporated therein from 5 to 50 parts byweight and preferably 10 to 30 parts by weight of an N-alkylarylsulfonamide of the formula wherein R1 is phenyl or tolyl radical andR2 is an alkyl radical containing at least 1 and not more than 8 carbonatoms. Thus, the novel fungicidal and bactericidal polyvinyl chloridecompositions of this invention are comprised of parts by weight of apolymerized vinyl chloride resin, 5 to 100 parts by Weight of aplasticizer, 0.1 to 2.5 parts by weight .of copper B-quinolinolate, and5 to 50 parts by weight and preferably 10 to 30 parts by weight of a.compound selected from the group, consisting of N-alkylbenzenesulfonamides and N-alkyl toluenesulfonamldes wherein the alkylgroup contains at least 1 and not more than 8 carbon atoms.

Typical of the N-alkyl arylsulfonamides which may be utilized in thenovel composition of this invention are the following:

Though particular reference has been made to compositions of polymerizedvinyl chloride resins. the herein described N-allnl benzenesulfonamidesand N-alkyl toluenesulionamides and copper 8- quinolinolate may beincorporated into composi-' tions containing resins that are formedthrough the conJoint polymerization of mixtures of monomers that arepredominantly vinyl chloride. such as mixtures of predominantly vinylchloride and varying amounts of winyl esters of carboxylic acids. Thesecopolymers containing predominantly combined vinyl chloride areexemplifiedby copolymers containing 95% to 80% by weight of combinedvinyl chloride and to 20% by weight of combined vinyl acetate, vinylfluoride, vinylidene chloride, diethyl maleate or methyl methacrylate.

The compositions of this invention may also contain carbon black, zincoxide, clay, wood flour,

and other pigments, stabilizers, and fillers commonly used in theplastics industry. The compatibilizing effect of the N-alkylbenzenesulfonamides and N-alkyl toluenesulfonamides of this invention oncopper 8-quinolinolate is also realizcd in unplasticized compositions aswell as compositions plasticized with the common plasticizers used inthe plastics industry such as dioctyl phthalate, dibutyl phthalate,dinonyl phthalate, tricresyl phosphate, trioctyl phosphate, dibutylsebacate, dioctyl adipate, butyl phthalyl, butyl glycolate, and resinousplasticizers such as the condensation products of polycarboxylic acidsand polyhydric alcohols.

Th0 novel compositions of this invention may be eifectively utilized toproduce free or unsupported polyvinyl chloride films and sheeting whichwill be resistant to the deteriorating eilects of fungi and bacteria.These compatible compositions may also be applied as a coating tovarious textiles, such as, cotton, wool, rayon, silk. and nylon, andsynthetic and artificial leathers. These compositions may be so appliedby any of the well known methods used to apply polyvinyl chloridecoatings, such as the conventional calendering, solvent coating, or dipcoating methods. Such coated compositions, wherein the novelcompositions of this invention are utilized, in addition to possessingthe desirable characteristics of the base material and the polyvinylchloride coating, are thereby rendered extremely resistant todeterioration due to attack by fungi and bacteria.

All of the compositions of the following examples were processed in thefollowing identical manner in order to evaluate the utility of theN-alkyl benzenesulfonamides and N-alkyl toluenesulfonamides of thisinvention as compatibilizing agents for copper B-quinolinolate inpolyvinyl chloride compositions. This processing procedure is describedas follows:

The proportional parts by weight of the resins, plasticizers,compatibilizing agent and copper 8- quinolinolate were weighed andintimately mixed, and the mixture placed on a differential speed rollmill and further mixed and fluxed for 5 minutes at 160C. At the end ofthis roll and mixing operation, homogeneous compositions had formed onthe roll mill and the plasticized polyvinyl chloride compositions werethen sheeted of! of the 'roll mill.. Specimens of each composition werethen placed in a mold 5" x 5" x 0.040" and subjected to a pressure of2,000 lbs. per square inch, and a temperature of 160 C. The moldedspecimens, after removal from the mold, were observed for compatibility.Those compositions which exhibited signs of blooming or crystallizationon the surface of the molded specimen were regarded as incompatible andunilt for use. Those specimens which evidenced no sign ofcrystallization or blooming, were regarded as compatible and suitablefor use.

Example I Example 11 A composition comprising parts of polyvinylchloride, 2.5 parts of tricresyl phosphate. 2.5 parts of butyl acetylricinoleate, 10 parts of N-methyl benzenesulfonamide and 1 part ofcopper 8-quinolinolate was processed in the above,

described .manner. The specimen when removed from the mold was free ofany signs of blooming or crystallization. thereby indicating acompatible composition.

Example III A composition comprising 100 parts of polyvinyl chloride, 25parts of tricresyl phosphate, 25 parts of butyl acetyl ricinoieate, and0.2 part of copper 8-quinolinolate was processed in the above describedmanner. The molded specimen exhibited blooming and a crystal formationon the surface thereby indicating that copper 8-quinolinolate wasincompatible in this composition.

Example IV A composition comprising 100 parts of polyvinyl chloride, 25parts of tricresyi phosphate, 25

parts of butyl acetyl ricinoleate, 5 parts of N-G- methylheptylbenzenesulfonamide and 0.2 part of copper 8-quinolinolate was preparedin the above described manner. The specimen exhibited no signs ofincompatibility.

Example V phosphate, 25 parts of butyl acetyl ricinoleate, 25

parts of N-ethyl p-toluenesulfonamide, and 1 part of copperfl-qulnolinolate and was processed in the manner described above. Themolded specimen evidenced no signs of incompatibility. A cotton duckfabric was coated with the composition described in Example V by thecalendering method which consisted in simultaneously passing the fabricand the polyvinyl chloride composition through a conventional threeroller calender. The coated cotton duck fabric. in addition topossessing the desirable characteristics of the fabric and the polyvinylchloride coating, was extremely resistant to attack by fungi-andbacteria by virtue of the composition having incorporated therein copperB-quinolinolate.

E 'cample VI 1 A composition comprising 100 parts of polyvinyl chloride,25 parts of dioctyl phthalate, and 2.5 parts of copper 8-quinolinolatewas prepared in the manner described above. The molded specimenexhibited blooming and crystallization on the surface indicating theincompatibility of copper 8-quinolinolate in this composition. "2

Example VII A composition was prepared containing 190 parts of polyvinylchloride, 25 parts of dioctyl phthalate, 50 parts of N -butylo-toluenesulfonamide. and 2.5 parts of copper 8-quinolinolate andprocessed in the above described manner. The

moldedspecimen evidenced no signs of incompatibility.

. Example VIII A composition was prepared containing 100 parts ofpolyvinyl chloride, 100 parts of dioctyl phthalate, and 1.5 parts ofcopper 8-quinolinolate and processed in the manner described above. Themolded specimen exhibited crystallization on the surface indicating theincompatibility of copper fl-quinolinolate.

Example IX A composition comprising 100 parts of polyvinyl chloride, 100parts of dioctyl phthalate, 30 parts of N-2-ethylhexylp-toluenesulfonamide and 1.5 parts ofcopper B-quinolinolate wasprocessed in the above described manner. The molded specimen exhibitedno signs of incompatibility.

Example X Example XI A composition comprising 100 parts of polyvinylchloride, 12.5 parts of dioctyl phthalate. 12.5 parts of butyl acetylricinoleate, 35 parts of N-hexyl benzenesulfonamide, and 2 parts ofcopper B-quinolinolate was processed in the above described manner. Themolded specimen exhibited no signs of incompatibility.

Example XII A composition comprising 100 parts of a polymerized vinylresin containing 90 parts of combined vinyl chloride and 10 parts ofcombined vinyl acetate. 25 parts of tricresyl phosphate. 25

vinyl chloride coating.

Penidlliumep 8 parts of butyl acetyl ricinoleatc. and 1.3111: of copperB-quinolinolate in theme described manner. The molded specimen exhibitedcrystallization on the-surface of the composition thereby indicatingtheincompatibility of copper s-quinolinolate. I

. Example XIII A composition comprising 100 parts of a polymerized vinylresin containing parts of com-; bined vinyl chloride and 10 parts ofcombined vinyl acetate. 25 parts of-tricresyl phosphate. 25 parts ofbutyl acetyl ricinoleate. 25 parts of N-isopropyl benzene'sulfonamide,and 1 part of copper squinolinolate was processed in the above describedmanner. The molded evidenced no signs ofincompatibility.

The composition described in Example was calendered onto a cottonfabric. The coated fabric was thereby rendered resistant to attack bysuch micro-organisms as fungi and bacteria and at the same timepossessed all the desirable characteristics of the base fabric and thepoly- E'rample XIV A composition comprising parts of a polymerized vinylresin containing 90 parts of combined vinyl chloride and lU- parts ofcombined vinyl acetate. 25 parts of. trictesyl phosphate, 25 parts ofbutyl acetyl ricinoleate,'25 parts of N-isopropylp-tolu'enesuli'onamide, and 1 part of copper 8-quinolinolate wasprocessed in the above described manner. The molded specimen evidencedno signs of incompatibility.

ExamplcsI,III,VI,VlII,I,andxIIasherein set forth very clearly indicatethe extreme incompatibility of copper B-quinolinolate in polyvinylchloride compositions as are prepared according'to the methodsheretofore practiced. Examples 11. VI. V, VII, IX, XI. XIII. and XIV areindicative of the outstanding compatibility eifect of the N-alkylbenzenesulfonamides and the N-alkyl toluenesulfonamides of thisinvention'on copper s-quinolinolate in polyvinyl chloride compositionsthereby permitting the formulation of polyvinyl chloride compositionswhich are resistant to deterioration due to attack by suchmicro-organisms as fungi and bacteria.

Samples of the polyvinyl chloride coated cotton fabric prepared inExamples V and XIII. and unsupported polyvinyl chloride p epared fromthe compositions set forth in Examples 11 and XIV were inoculated witheach of the following organisms: v

Chaetomium alobosum, Metarrhizium sp., 4:- perpillus nicer andPenicillium ap. and then incubated for 36 hours.

Results of this biological test were as follows:

Organism Fungus Activity on the Sample Clladnmlum 1060mm.-. No wthoftbeorgnnismonthesam Melarrlizia m rp pk Aspemi'llus nioer- Do A furtherunsupported polyvinyl "chloride film was prepared containing 100 partsof polyvinyl chloride and 50 parts of butyl acetyl ricinoleate. Whenthis composition was inoculated with the above mentioned organisms, asevere growth of the organism took place on the sample. indicating theoutstanding fungi and bacteria resistant characteristics of the novelcompositions of this invention.

I claim:

1. A composition comprising 100 parts by weight a polymerized vinylresin containing at least 80% of combined vinyl chloride, a plasticizerfor said resin, 0.1 to 2.5 parts by weight of copper 8- quinolinolate,and 5 to 50 parts by weight oi a compound selected from the groupconsisting of N-alkyl benzenesulionamides and N-aikyitoluenesulionamides wherein the alkyl substituent contains at least 1and not more than 8 carbon atoms.

2. A composition comprising 100 parts by weight 0! a polymerized vinylresin containing at least 80% 0! combined vinyl chloride, a plasticizerfor said resin, 0.1 to 2.5 parts by weight of copper B-quinclinolate,and 10 to 30 parts by weight of a compound selected from the groupconsisting of N-alkyi benzenesulionamides and N-alkyltoluenesuiionamides wherein the alkyl substituent contains at least 1and not more than 8 carbon atoms.

3. A composition comprising 100 parts by weight of a polymerized vinylresin containing at least 80% of combined vinyl chloride, a plasticizerfor said resin, 0.1 to 2.5 parts by weight of copper B-quinolinolate and10 to 30 parts by weight of N-ethyl p-toluenesuli'onamide.

4. A composition comprising 100 parts by weight oi a polymerized vinylresin containing at least 80% of combined vinyl chloride, aplasticizerfor said resin, 0.1 to 2.5 parts by weight of copper a-quinolinolate,and 10 to 30 parts by weight of N-isopropyi benzenesulionamide.

Certificate of Correction Patent No. 2,567,905

It is hereby the above numbered patent 5. A composition comprising 100parts by weight of a polymerized vinyl resin containing at least ofcombined vinyl chloride, a plasticizer for said resin, 0.1 to 2.5 partsby weight of copper 8-quinolinolate, and 10 to' 30 parts by weight ofN-isopropyl p-toluenesulionamide.

6. An article of manufacture comprising a textile coated with thecomposition of claim 1.

'7. An article of manufacture comprising a textile coated with thecomposition of claim 2.

8. An article oi manufacture comprising a textile coated with thecomposition of claim 3.

9. An article of manufacture comprising a textile coated with thecomposition oi claim 4.

10. An article 01' manufacture comprising a textile coated with thecomposition of claim 5.

WALTER E. FIELD.

REFERENCES CITED The following references are of record the file of thispatent:

UNITED STATES PATENTS OTHER REFERENCES Paint Mfg Jan. 1948, 18, 1, pp.21 and 22.

September 11, 1951 WALTER E. FIELD certified that error appears in theprinted specification of requiring correction as Column 6, line 40, forV1 read IV;

follows and that the said Letters Patent should be read as correctedabove, so that the same may conform to the record of the case in thePatent Oflice.

Signed and sealed this 11th day of December,

THOMAS F. MURPHY,

I claim:

1. A composition comprising 100 parts by weight a polymerized vinylresin containing at least 80% of combined vinyl chloride, a plasticizerfor said resin, 0.1 to 2.5 parts by weight of copper 8- quinolinolate,and 5 to 50 parts by weight oi a compound selected from the groupconsisting of N-alkyl benzenesulionamides and N-aikyitoluenesulionamides wherein the alkyl substituent contains at least 1and not more than 8 carbon atoms.

2. A composition comprising 100 parts by weight 0! a polymerized vinylresin containing at least 80% 0! combined vinyl chloride, a plasticizerfor said resin, 0.1 to 2.5 parts by weight of copper B-quinclinolate,and 10 to 30 parts by weight of a compound selected from the groupconsisting of N-alkyi benzenesulionamides and N-alkyltoluenesuiionamides wherein the alkyl substituent contains at least 1and not more than 8 carbon atoms.

3. A composition comprising 100 parts by weight of a polymerized vinylresin containing at least 80% of combined vinyl chloride, a plasticizerfor said resin, 0.1 to 2.5 parts by weight of copper B-quinolinolate and10 to 30 parts by weight of N-ethyl p-toluenesuli'onamide.

4. A composition comprising 100 parts by weight oi a polymerized vinylresin containing at least 80% of combined vinyl chloride, aplasticizerfor said resin, 0.1 to 2.5 parts by weight of copper a-quinolinolate,and 10 to 30 parts by weight of N-isopropyi benzenesulionamide.

Certificate of Correction Patent No. 2,567,905

It is hereby the above numbered patent 5. A composition comprising 100parts by weight of a polymerized vinyl resin containing at least ofcombined vinyl chloride, a plasticizer for said resin, 0.1 to 2.5 partsby weight of copper 8-quinolinolate, and 10 to' 30 parts by weight ofN-isopropyl p-toluenesulionamide.

6. An article of manufacture comprising a textile coated with thecomposition of claim 1.

'7. An article of manufacture comprising a textile coated with thecomposition of claim 2.

8. An article oi manufacture comprising a textile coated with thecomposition of claim 3.

9. An article of manufacture comprising a textile coated with thecomposition oi claim 4.

10. An article 01' manufacture comprising a textile coated with thecomposition of claim 5.

WALTER E. FIELD.

REFERENCES CITED The following references are of record the file of thispatent:

UNITED STATES PATENTS OTHER REFERENCES Paint Mfg Jan. 1948, 18, 1, pp.21 and 22.

September 11, 1951 WALTER E. FIELD certified that error appears in theprinted specification of requiring correction as Column 6, line 40, forV1 read IV;

follows and that the said Letters Patent should be read as correctedabove, so that the same may conform to the record of the case in thePatent Oflice.

Signed and sealed this 11th day of December,

THOMAS F. MURPHY,

1. A COMPOSITION COMPRISING 100 PARTS BY WEIGHT OF A POLYMERIZED VINYLRESIN CONTAINING AT LEAST 80% OF COMBINED VINYL CHLORIDE, A PLASTICIZERFOR SAID RESIN, 0.1 TO 2.5 PARTS BY WEIGHT OF COPPER 8-QUINOLINOLATE,AND 5 TO 5- PARTS BY WEIGHT OF A COMPOUND SELECTED FROM THE GROUPCONSISTING OF N-ALKYL BENZENESULFONIAMIDES AND N-ALKYLTOLUENESULFONAMIDES WHEREIN THE ALKYL SUBSTITUENT CONTAINS AT LEAST 1AND NOT MORE THAN 8 CARBONS ATOMS.